Nitro-amino diisocyanates



' United States Patent NITRO-AMINO DIISOCYANATES Karl Klager, Monrovia, and Milton B. Frankel, Pasadena, Calif., assignors to Aerojet-General Corporation, Azusa, Califl, a corporation of Ohio N0 Drawing. Filed Oct. 25, 1954, Ser. No. 464,609

12Claims. (Cl. 260-453) This invention relates to a new class of bi-functional polynitro compounds and more particularly it relates to anew series of nitro-amino diisocyanates having the general formula:

Lt... .I. L 10.1

wherein R is a lower 'alkylene radicaLand x is a small whole number from 1 to 3 inclusive.

The compounds of the present invention find valuable use as intermediates in the preparation of high explosives and solid propellant compositions. They readily condense with nitroalkanols such as 2,2,2-trinitroethanol to form-highly nitrated polyurethanes. This procedure is described in detail in assignees copending application "ice 2 limes? l invention are conveniently prepared by reacting a dinitro- No. 464,610 filed concurrently with the present application. These compositions are useful as high explosives and as such can be used as the explosive charge in the warhead of any conventional explosive missile, projectile, rocket, or the like. Such a device is disclosed in US. Patent No. 2,470,162. The diisocyanatesof this invention also condense with nitro-substituted polyhydric alcohols to form high molecular weight polyurethane resins which are themselves useful as solid propellant compositions. p a

The art, for many years, has recognized the valuable properties of certain related nitro-substituted organic compounds for use as explosives and propellants, however the carbo-nitro groupings of these compounds are relatively unstable, rendering their production and handling both diflicult and hazardous. The compounds of the present invention, possessing the stabilizing nitroamino groups, may be manufactured with greater ease and also possess a much higher specific impulse than the less stable carbonitro compounds heretofore commonl used. 7

The preparation of the polynitro nitro-amino diisocyanates of the present invention proceeds in accordance with the general reaction scheme set forth below:

Lt... .L L

'l Ito. J.

hydroxy ester with ammonia and subsequently nitrating the resultant product with nitric acid. These procedures are more fully described in our copending applications Nos. 416,381 and 416,382 filed March 15, 1954, now both abandoned.

The following examples are provided to more clearly define the invention:

EXAMPLE I Preparation of 4,4,6,8,8-pentanitro-6-aza-undecanedioic acid In a one-liter Erlenmeyer flask was placed 85 gms. (0.18 mole) of dimethyl-4,4,6,8,8-pentanitro-6-aza-undecanedioate and 500 ml. of concentrated hydrochloric acid. The mixture Was heated on a steam bath for 1.5 hours. The solid was collected, washed with water, and recrystallized from methanol and water to give 50.0 gms.

(80.0%) of 4,4,6,8,8 pentanitro 6 aza-undecanedioic Preparation of 4,4,6,8,8 pentanitro-o-aza-undecanedioyl chloride In a -ml. Erlenmeyer flask was placed 3.0 gms.

(0.0068 mole) of 4,4,6,8,8-pentanitro-6-aza-undecanedioic acid and 3 m1. of phosphorous oxychloride.

I Enough phosphorous pentachloride was added to give a solution when the reaction mixture was warmed on the steam bath. The solution was heated on the steam bath for 10 minutes and benzene was added to precipitate 2.0 gms. (61.4%) of the white solid. The product was purified by dissolving in phosphorous oxychloride and reprecipitating with hexane, melting point 152-155. C, I.S.=-100 cm./2 k-g.

Analysis.Calcd. for CmHmNsOmClzi %C, %H, 2.53; %N, 17.54; %Cl, 14.90. Found: %C, 25.43; %H, 3.04; %N, 19.38; %Cl, 13.84. p L

EXAMPLE III In a 500-ml. B-necked flask, fitted with a mechanical stirrer and thermometer, was placed 12.5 gms: of crude 4,4,6,8,8-pentanitro '6 aza-undecanedioyl chloride,

ml. of glacial acetic acid and 10 gms. of sodium azide The reaction mixture was stirred for one hour at 15-20 C. no heat of reaction was evident. Methylene chloride, 150 ml., was added and the mixture was washed with water, 1% sodium bicarbonate, and water. The methyl-' chloroform was added to the solid and the solution 1 Patented Apr. 4,1 1961 refluxed for two hours with the evolution of 0.5 liter of 2. As a composition of matter, 3,3,5,7,7-pentanitro-5- nitrogen gas. The solution was concentrated in vacuo aza-nonane-1,9-diisocyanate having the formula:

leaving a brown solid. The product was dissolved in N0, o, No,

dioxane and repreclprtated with carbon tetrachloride.

Recrystallization from chloroform gave a white crystal- 5 line solid, melting point 92-95 C. No?

Analysis.--Calcd. for C H N O %C, 27.53; %H, 3. As a composition of matter, 3,3,5,5,7,9,9,11,11- 2.77; %N, 25.69. Found: %C, 28.38; %H, 3.22; %N, nonanitro-7-aza-tridecane 1,13 diisocyanate having the 25.71. formula:

By utilizing as starting materials the esters of 4,4,6,8,8- N0, N0; N0, N0, N0; pentanitro-6-aza-undecane-1,1l-dioic acid, 5,5,7,9,9-penta- O:O=N OH1CHT GH2 0H2 N OHTGOHTGGHIOHTN=O=O nitro-7-aza-tridecane-1,13-dioic acid, 6,6,8,10,10-pentanitro-S-aza-pentadecane- 1,15-dioic acid, 4,4,6,6,8,10,l0, N02 N02 12,l2-nonanitro-8-aza-pentadecane-l,15-dioic acid and 4, s a composition of matter, -p nt tr0- 4,6,6,8,8,10,12,12,14,14,16,16 tridecanitro-lO aza-nonaaza-undecane-l.ll-diisocyanate. having the f m decane-l,19-dioic acid and proceeding in accordance with Y the examples set forth above, one obtains the correspond ing diisocyanates, namely, 3,3,5,7,7-pentanitro-5-aza- (LC-N4}HQOHZOHrifHrNaHT;)GHCHCH NC'0 nonane-1,9-diisocy-anate, 4,4,6,8,8-pentanitro-6-aza-undecane-1,1l-diisocyanate, 5,5,7,9,9-pentanitro-7 aza-tride- 5. As a composition of matter, 3,3,5,5,7,7,9,11,11,13, cane-1,13-diisocyanate, 3,3,5,5,7,9,9,11,11 nonanitro-7- 13,15,15 tridecanitro 9 aza-heptadecane-l,17-diisocyaza-tridecane-l,13-diisocyanate and 3,3,5,5,7,7,9,11,11,13, anate having the formula:

NO: NO: N02 N02 N02 N02 No:

NO: NO: N02 N02 NO: N01 13,15,15-tridecanitro 9 aza heptadecane 1,17 diiso- 6. As a composition of matter, 5,5,7,9,9-pentanitro-7- cyanate respectively. p aza-tn'decane-l,13-diisocyanate having the formula:

N01 N02 Thus it may be seen, from the foregoing examples that 7. The process for preparing nitroamino diisocyanates a wide variety of diisocyanates can be prepared by means having the general formula: of the procedure recited above by simply selecting ap- O: "I IITO; N01 "l propriate starting materials. N CH C =0 It should be understood that the examples set forth Ll T L J 0 above are provided in only an illustrative sense and are not intended to impose any limitations upon the scope 40 which comprises reacting a dibasic acid halide having the general formula:

of the invention.

The diisocyanates of this invention readily condense f 1 I No? I with nitroalkanols such as 2,2,2-trinitroethanol in the X-O-RCCHz--N--CHz- --R-CX presence of a condensation catalyst such as boron tri- L L L L 1 i fluoride to form? higijly Pitrated polyurethanes dwhjch 5 wherein R is a lower alkylene radical, x is a small whole are useful as high explosives. These compoun s can number from 1 to 3 inclusive and X is halogen, with used in any conventional explosive missile sodium azide and heating to effect rearrangement to the jectile, rocket, or the like, as the main explosive charge. desired diisocyanam An example of such a missile is disclosed in United 8. A method of preparing 3,3,sl7,7 pentanitro s aza States 1Sued one nonane diisocyanate which comprises reacting 4,4,6,8,8- Way h high exploslvis m a dime? Such as pentanitro-6-aza-undecane-1,1l-dioic acid halide with sothat dlsclosed 1n United States Patent No. 2,470,162, dium azide heath!y to efiect rearrangement to the is to pack the crystalline explosive in powder form diisocyanate into the warhead of the missile. Alternatively, the A meihod of preparing 3,3,55,79,941,11 nona ciystals can be first .pcugtlzeid then. f A nitro-7-aza-tridecane diisocyanate which comprises reactc arge thus prepare? 1S .sufficlenily .msensmve with" ing 4,4,6,6,8,10,10,12,12-nonanitro 8 aza-pentadecane- Stand the Shock entalled m the electlon 9 a Shell from 1,15-dioic acid halide with sodium azide and heating to a gun barrel or from a rocket launchlng tube under efiect management to the diisocyamnfi the pressure developed from ignition of a propellant A method of preparing 4,468,8 pentanitm 6 am i i be gamed eiiplodfie g i undecane diisocyanate which comprises reacting 5,5,7,9,9- an lmpac or use'mec amsm mg a 6 ma mg pentanitro-7-aza-tridecane-1,13-dioic acid halide with soexplqsive F f azide. or {nerfury fulminate' dium azide and heating to effect rearrangement to the This application is a contmuahon-m-part of our codiisocyanate pendmg application filed August 1953 11. The method of preparing 5,5,7,9,9-pentanitro-7-azanow i f v tridecane diisocyanate which comprises reacting 6,6,8,10, Y i th 10 pentanitro 8 aza-pentadecane-l,IS-dioic acid halide anajtes f g 2 32 2 ggg Intro-ammo usocy' with sodium azide and heating to efiect rearrangement to g g the diisocyanate.

12. A method of preparing 3,3,5,5,7,7,9,11,11,13,13, F F 1 i r i I 15,15-tridecanitro-9-aza-heptadecane diisocyanate which O:C=N"'RCGH1'NCHFC RN=9:0 comprises reacting 4,4,6,6,8,8,10,12,12,14,l4,l6,16-tridec- L iro, J, L o, anitro-lO-aza-nonadecane-l,l9-dioic acid halide with sodium azide and heating to effect rearrangement to the wherein R is a lower alkylene radical and x is a small diisocyanate. whole number from 1 to 3 inclusive. No references cited. 

1. AS COMPOSITIONS OF MATTER THE NITRO-AMINO DISOCYANATES HAVING THE GENERAL FORMULA: 